EP0167488B1 - Ionisch modifizierte Polysaccharide, Verfahren zu deren Herstellung und deren Verwendung - Google Patents
Ionisch modifizierte Polysaccharide, Verfahren zu deren Herstellung und deren Verwendung Download PDFInfo
- Publication number
- EP0167488B1 EP0167488B1 EP85810285A EP85810285A EP0167488B1 EP 0167488 B1 EP0167488 B1 EP 0167488B1 EP 85810285 A EP85810285 A EP 85810285A EP 85810285 A EP85810285 A EP 85810285A EP 0167488 B1 EP0167488 B1 EP 0167488B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polysaccharide
- formula
- modified
- alkyl
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000004676 glycans Chemical class 0.000 title claims abstract description 116
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 116
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims description 30
- 238000002360 preparation method Methods 0.000 title claims description 8
- 229920001353 Dextrin Polymers 0.000 claims abstract description 11
- 239000004375 Dextrin Substances 0.000 claims abstract description 11
- 235000019425 dextrin Nutrition 0.000 claims abstract description 11
- 229920002307 Dextran Polymers 0.000 claims abstract description 8
- 229920000936 Agarose Polymers 0.000 claims abstract description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 52
- 230000005526 G1 to G0 transition Effects 0.000 claims description 23
- -1 methylol compound Chemical class 0.000 claims description 14
- 238000006467 substitution reaction Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 238000004587 chromatography analysis Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 150000002825 nitriles Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 3
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical group NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 238000007259 addition reaction Methods 0.000 claims 1
- 125000005466 alkylenyl group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000002002 slurry Substances 0.000 description 21
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 20
- 238000013375 chromatographic separation Methods 0.000 description 20
- 239000004021 humic acid Substances 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229920001732 Lignosulfonate Polymers 0.000 description 16
- 239000000470 constituent Substances 0.000 description 15
- 150000001720 carbohydrates Chemical class 0.000 description 14
- 239000000975 dye Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000005342 ion exchange Methods 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000008961 swelling Effects 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 238000011049 filling Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 230000033228 biological regulation Effects 0.000 description 7
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- NJIRSTSECXKPCO-UHFFFAOYSA-M 3-[n-methyl-4-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]anilino]propanenitrile;chloride Chemical compound [Cl-].C1=CC(N(CCC#N)C)=CC=C1\C=C\C1=[N+](C)C2=CC=CC=C2C1(C)C NJIRSTSECXKPCO-UHFFFAOYSA-M 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229960002449 glycine Drugs 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 description 3
- HZWLVUKHUSRPCG-BJIHTTGYSA-M sodium;(6r,7r)-3-(acetyloxymethyl)-7-[(5-amino-5-carboxypentanoyl)amino]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate Chemical class [Na+].S1CC(COC(=O)C)=C(C([O-])=O)N2C(=O)[C@@H](NC(=O)CCCC(N)C(O)=O)[C@@H]12 HZWLVUKHUSRPCG-BJIHTTGYSA-M 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 2
- 108010077895 Sarcosine Proteins 0.000 description 2
- 229920005654 Sephadex Polymers 0.000 description 2
- 239000012507 Sephadex™ Substances 0.000 description 2
- 229920002684 Sepharose Polymers 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- RFQSMLBZXQOMKK-UHFFFAOYSA-N [3-[(4,8-diamino-6-bromo-1,5-dioxonaphthalen-2-yl)amino]phenyl]-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC(NC=2C(C3=C(N)C=C(Br)C(=O)C3=C(N)C=2)=O)=C1 RFQSMLBZXQOMKK-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000539 amino acid group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-O hydron piperazine Chemical compound [H+].C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-O 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000019357 lignosulphonate Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229940043230 sarcosine Drugs 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HZWLVUKHUSRPCG-OOARYINLSA-M sodium;(6r,7r)-3-(acetyloxymethyl)-7-[[(5r)-5-azaniumyl-5-carboxylatopentanoyl]amino]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate Chemical compound [Na+].S1CC(COC(=O)C)=C(C([O-])=O)N2C(=O)[C@@H](NC(=O)CCC[C@@H]([NH3+])C([O-])=O)[C@@H]12 HZWLVUKHUSRPCG-OOARYINLSA-M 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 description 1
- DCQFFOLNJVGHLW-ZNVMLXAYSA-N (1s,4s,5r,8r)-2,6-dioxabicyclo[3.2.1]octane-3,4,8-triol Chemical compound O[C@H]1[C@@]2([H])OC[C@]1([H])OC(O)[C@H]2O DCQFFOLNJVGHLW-ZNVMLXAYSA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- CWZMSJKUTBPRGA-UHFFFAOYSA-N 1h-benzimidazole;4,5-dihydro-1h-imidazole Chemical compound C1CN=CN1.C1=CC=C2NC=NC2=C1 CWZMSJKUTBPRGA-UHFFFAOYSA-N 0.000 description 1
- HMBWLZFUIVAXTO-UHFFFAOYSA-N 2-[benzyl(carboxymethyl)amino]but-3-enoic acid Chemical compound OC(=O)CN(C(C=C)C(O)=O)CC1=CC=CC=C1 HMBWLZFUIVAXTO-UHFFFAOYSA-N 0.000 description 1
- WFISPRWLCFTIRC-UHFFFAOYSA-N 2-dimethoxyphosphoryl-n-(hydroxymethyl)propanamide Chemical compound COP(=O)(OC)C(C)C(=O)NCO WFISPRWLCFTIRC-UHFFFAOYSA-N 0.000 description 1
- TXPKUUXHNFRBPS-UHFFFAOYSA-N 3-(2-carboxyethylamino)propanoic acid Chemical compound OC(=O)CCNCCC(O)=O TXPKUUXHNFRBPS-UHFFFAOYSA-N 0.000 description 1
- SZUZWFXRVSNBOZ-UHFFFAOYSA-N 3-[2-(2-carboxyethylamino)ethylamino]propanoic acid Chemical group OC(=O)CCNCCNCCC(O)=O SZUZWFXRVSNBOZ-UHFFFAOYSA-N 0.000 description 1
- UHVIHQSYQVURFV-UHFFFAOYSA-N 4,6-dichlorotriazin-5-amine Chemical compound NC1=C(Cl)N=NN=C1Cl UHVIHQSYQVURFV-UHFFFAOYSA-N 0.000 description 1
- ZMWAXVAETNTVAT-UHFFFAOYSA-N 7-n,8-n,5-triphenylphenazin-5-ium-2,3,7,8-tetramine;chloride Chemical compound [Cl-].C=1C=CC=CC=1NC=1C=C2[N+](C=3C=CC=CC=3)=C3C=C(N)C(N)=CC3=NC2=CC=1NC1=CC=CC=C1 ZMWAXVAETNTVAT-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 description 1
- JLYINULMTZGQAU-UHFFFAOYSA-N ClC1=CC=[N+](Cl)N=N1 Chemical group ClC1=CC=[N+](Cl)N=N1 JLYINULMTZGQAU-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- GDFAOVXKHJXLEI-UHFFFAOYSA-N N-methylalanine Chemical compound CNC(C)C(O)=O GDFAOVXKHJXLEI-UHFFFAOYSA-N 0.000 description 1
- XLGQCRNGCAPVLP-UHFFFAOYSA-N N=CC(=O)O.C(CC)(=O)O Chemical compound N=CC(=O)O.C(CC)(=O)O XLGQCRNGCAPVLP-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005377 adsorption chromatography Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229920006321 anionic cellulose Polymers 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 235000010633 broth Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 125000004803 chlorobenzyl group Chemical group 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical group NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-O morpholinium Chemical compound [H+].C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-O 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- ORTFAQDWJHRMNX-UHFFFAOYSA-M oxidooxomethyl Chemical compound [O-][C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-M 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001302 tertiary amino group Chemical class 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
- C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3206—Organic carriers, supports or substrates
- B01J20/3208—Polymeric carriers, supports or substrates
- B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
- B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
- B01J20/3221—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond the chemical bond being an ionic interaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
- B01J20/3251—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulphur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
- B01J20/3253—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure not containing any of the heteroatoms nitrogen, oxygen or sulfur, e.g. aromatic structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
- B01J20/3255—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. heterocyclic or heteroaromatic structures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/14—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
Definitions
- the present invention relates to chemically ionically modified, i.e. cationic, amphoteric or anionically modified polysaccharides.
- the present invention therefore relates to chemically modified polysaccharides obtainable from crosslinked dextrin, optionally crosslinked dextran or optionally crosslinked agarose, which are characterized in that they have ⁇ -glycosidic linkages and via the grouping of the formula have ionic constituents bonded to the polysaccharide constituent, the carbonyl group being connected to the ionic constituent and the oxygen atom being connected to the polysaccharide constituent.
- a-glycosidically linked polysaccharides come above all starch and its derivatives such as Dextran and the dextrins, especially white dextrin, into consideration.
- a-glycosidically linked polysaccharides are possible, e.g. Agarose, which consists of alternating units of ⁇ -1,3-linked D-galactopyranose and a-1,4-linked 3,6-anhydro-L-galactopyranose.
- the polysaccharides according to the invention can be completely or partially crosslinked. Uncrosslinked dextrins, optionally crosslinked dextran or optionally crosslinked agarose, which are ionically modified and have a-glycosidic linkages, are of primary interest.
- the ionic constituents (substituents) in the modified polysaccharides according to the invention which are linked to the polysaccharide via the carbonyl group of the grouping of the formula (1), are present as anionic, preferably amphoteric and in particular cationic constituents.
- Such ingredients are cationic, contain basic substituents such as e.g. quaternary guanidinium, immonium or especially ammonium groups.
- basic substituents such as e.g. quaternary guanidinium, immonium or especially ammonium groups.
- cationic constituents which preferably contain substituted ammonium groups, usually two such ammonium groups being present or, above all, such an ammonium group being present.
- N-substituents are aliphatic, cycloaliphatic, aromatic and araliphatic groups which, if appropriate, can preferably form 5-membered, especially 6-membered rings together with the nitrogen and optionally further heteroatoms.
- Straight-chain or branched lower alkyl radicals are particularly suitable as N-substituents, such lower alkyl radicals optionally being substituted by hydroxyl, nitrile, halogen or lower alkoxy.
- R "R 2, R 3 and R 4 are each independently hydrogen, unsubstituted or substituted by hydroxyl, nitrile, halogen or C 1 -C 4 -alkoxy-substituted, straight or branched C, -C 4 alkyl, unsubstituted or substituted by C I -C 4 alkyl, cycloalkyl, unsubstituted or nitro or halogen substituted benzyl or phenyl, or R, and R 2 together with the nitrogen atom connecting them and optionally further in the hetero atom a 5- or 6-membered heterocyclic ring or R 3 and R 4 together with the grouping connecting them and optionally further heteroatoms are also a 5- or 6-membered ring and Q and Q 2 are each, independently of one another, alkylene having 1 to 8 carbon atoms
- Preferred aliphatic N substituents are optionally branched lower alkyl radicals which are optionally substituted by nitrile, especially hydroxyl or chlorine, as halogen.
- cycloaliphatic N-substituents are e.g. Cyclopentyl and especially cyclohexyl, which are optionally substituted with lower alkyl.
- halogen e.g. Chlorine-substituted or, above all, unsubstituted benzyl or phenyl are preferred as araliphatic and aromatic N-substituents.
- the heterocyclic rings which can be formed together with the nitrogen atom of an ammonium group or the two nitrogen atoms of two ammonium groups and optionally further heteroatoms, in particular further nitrogen and / or oxygen atoms, are preferably e.g. Pyrrolidinium, piperidinium, morpholinium, imidazolinium, benzimidazolinium, especially piperazinium and especially triazinium rings, which are optionally substituted by halogen, e.g. Chlorine, are substituted.
- the ammonium group is connected to the carbonyl group of the group of formula (1) preferably via an isopropylene, especially n-propylene, preferably ethylene group. This also applies if there are two ammonium groups for the connecting link between these two ammonium groups.
- preferred, cationically modified, polysaccharides according to the invention have basic radicals of the formula where n 1 or 2, R 5 , R 6 , R 7 and R 8 independently of one another are each hydrogen, alkyl, hydroxyalkyl, cyanoalkyl or chloroalkyl each having 1 to 4 carbon atoms, unsubstituted or substituted by C I -C 4 alkyl or cyclohexyl, unsubstituted benzyl, chlorobenzyl, unsubstituted phenyl, nitrophenyl or chlorophenyl, or R s and R 6 together with the nitrogen atom connecting them and optionally an oxygen atom, a pyrrolidinium, piperidinium or morpholinium ring, or R 7 and R 8 together with them connecting grouping and optionally further heteroatoms form an imidazolinium-benzimidazolinium, piperazinium, triazinium or mono- or dichlorotriazinium ring and
- cationically modified polysaccharides the basic residues of which contain a single ammonium group which is connected to the carbonyl group of the group of formula (1) via an ethyl group and which have two unsubstituted lower alkyl residues or one t-butyl residue substituted by hydroxyl as N-substituents .
- Such modified polysaccharides have, in particular, basic radicals of the formula or in which Rg and R 10 are different from one another or preferably the same and each is isopropyl, or in particular n-propyl, ethyl or methyl.
- amphoteric constituents which are linked to the carbonyl group of the grouping of the formula (1)
- amphoteric constituents generally contain zwitterionic, amino acid groups, for example aminoacetic acid (glycine), iminodiacetic acid, methylaminoacetic acid ( Sarcosine) methylaminopropionic acid, iminodipropionic acid, iminoacetic acid propionic acid, aspartic acid, ethanolaminoacetic acid, vinylbenzyliminodiacetic acid or ethylenediamine-N, N'-dipropionic acid groups.
- aminoacetic acid glycine
- iminodiacetic acid methylaminoacetic acid ( Sarcosine) methylaminopropionic acid
- iminodipropionic acid iminoacetic acid propionic acid
- aspartic acid ethanolaminoacetic acid
- vinylbenzyliminodiacetic acid or ethylenediamine-N, N'-dipropionic acid
- amino acid groups are preferably on the carbonyl group with the grouping of the formula (1) via an alkyl-substituted, phenyl-substituted or unsubstituted alkylene or phenylene chain and optionally additionally an oxygen or nitrogen atom or a secondary or alkyl-substituted tertiary amino group.
- the zwitterionic residues of preferred amphoteric constituents of the modified polysaccharides according to the invention thus correspond, for example, to the formula where X is -0-, ⁇ S ⁇ , or the direct bond, R 11 is hydrogen or alkyl having 1 to carbon atoms, Q 5 is an unsubstituted or C 1 ⁇ C 4 alkyl or phenyl substituted C 1 ⁇ C 8 alkylene or phenylene radical, Z, ⁇ B ⁇ COO ⁇ , alkyl having 1 to 4 carbon atoms or hydrogen, and a and B each independently represent an unsubstituted or C 1 -C 4 alkyl, C l -C 4 alkoxy or phenyl-substituted C 1 -C 8 alkylene radical.
- X in formula (6) preferably represents the direct bond and Z, lower alkyl, preferably methyl or ethyl, or hydrogen. Unsubstituted lower alkylene is the preferred definition of Q s .
- amphoteric modified polysaccharides those in the foreground of interest are the residues of the formula have, wherein Z 2 is methyl or hydrogen.
- such anionic constituents generally contain a carboxyl radical or acid radicals of a polybasic, inorganic, oxygen-containing acid, for example the radicals of a sulfuric acid ester or phosphoric acid ester, a phosphonic acid or phosphoric acid residue, a phosphoric acid half ester residue or a sulfonic acid residue.
- acidic radicals are generally linked directly to the carbonyl group of the grouping of the formula (1), preferably via an alkyl-substituted or unsubstituted alkylene or phenylene chain.
- the acidic residues of preferred anionic constituents of the modified polysaccharides according to the invention thus correspond, for example, to the formula wherein Y 1 ⁇ carboxyl or the acid residue of a polybasic, inorganic, oxygen-containing acid and Q s has the meanings given, acid residues of the formula wherein Q 6 is isopropylene, n-propylene, preferably ethylene or methylene and mean and R 11 has the indicated meanings are in the foreground of interest.
- the ionically modified polysaccharides according to the invention generally have a degree of substitution of about 0.1 to about 0.8, preferably 0.2 to 0.6.
- the degree of substitution is determined on the basis of the nitrogen content of the modified polysaccharide.
- N-methylol compounds for example, those of the formula or used, wherein A, Q 1 , Q 2 , Q 5 , R 1 , R 2 , R 3 , R 4 , X, Y, 6 , Z 1 and n have the meanings given.
- the compounds of formula (10) are described in German Offenlegungsschriften 2,650,966 and 1,650,999, the compounds of formula (11) in German Offenlegungsschrift 2,727,755 and the compounds of formula (12) in German Offenlegungsschrift 2 925 689 .
- the preparation of the compounds of the formulas (10), (11) and (12) is also described in the aforementioned German Offenlegungsschriften.
- Q 2 in formula (2), Q 4 in formula (3) and Q 5 in formula (6) are each for ethylene and X in formula (6) for are direct bond, the polysaccharide of the type mentioned first with methylolacrylamide as the methylol compound (prepared from acrylamide and formaldehyde or a formaldehyde-donating agent such as, for example, paraformaldehyde, hexamethylenetetramine or trioxane at a maximum of 100 ° C., preferably 20 to 60 ° C.
- non-ionic components of the formula has a cationic compound of the formula wherein n, R 1 , R 2 , R3, R 4 and Q 1 have the meanings given, an amphoteric compound of the formula wherein A and Z 1. have the meanings given, or an anionic compound of the formula wherein Y 1 ⁇ has the meanings given, the ionic component is introduced.
- a basic catalyst such as sodium hydroxide, sodium methylate or magnesium oxide
- the polysaccharide of the type specified is preferably kept under stirring with the methylol compound of one of the formulas (10), (11) or (12) in aqueous medium at pH 3 to 6 and 15 to 25 ° C. for about 20 to 40 minutes, then at 70 to 80 ° C dried and finally subjected to a heat treatment at 90 to 150 ° C, preferably 90 to 100 ° C, for about 1 to 2 hours.
- a polymerization inhibitor such as hydroquinone for about 20 to 40 minutes Stirred
- the ionically modified polysaccharides according to the invention are used for the purification of waste water, as is the case for ionically modified cellulose materials, e.g. is described in German Offenlegungsschrift 2,650,988, and in particular for separating substance mixtures which have at least a proportion of ionic components.
- the chromatographic separation process of such substance mixtures which is known per se, is characterized in that the ionically modified polysaccharides according to the invention, which have an ion exchange capacity, are used as the stationary phase.
- organic substance mixtures of any composition can be separated into their components, provided that at least one of the components of the substance mixtures is cationically, anionically or amphoterically charged.
- possible substance mixtures include technical mixtures of dyes, pharmaceuticals (preparation or purification of fermentation broths) and lignin derivatives mentioned.
- amino acid mixtures such as those e.g. present in preparations of crude cephalosporin C sodium salts can be purified by means of ion-exchange chromatography using the ionically modified polysaccharides according to the invention as the stationary phase.
- lignin amines or of lignin sulfonates which are contained in black liquors from wood pulping for paper production (power process) or in sulfite waste liquors from wood pulping (sulfite process).
- Such lignosulfonate mixtures are commercially available under the brand names such as ATTISOL® I and 11, MARASPERSE®, DYNASPERSE®, LIGNOSOL® D 10, BORRESPERSE @ N, POLYFON O 0 and H and REAX D 80L, 81A, 82, 83A, 85A and 88B available.
- Commercial lignin amine mixtures are also available, for example, under the brand names INDULIN® W1 and MOK.
- the most important advantage of the ionically modified polysaccharides according to the invention is that, thanks to their good separation properties and their good flow behavior, they can be used perfectly as a stationary phase in chromatographic separation processes, the entire pH range of pH being approximately using both alkaline and acidic eluents 1 to about 14 can be used.
- reaction mixture is heated to 55 ° C., held at this temperature for 15 hours, then cooled to 20 ° C. and adjusted to a pH of 9.5 with a 37% strength aqueous hydrochloric acid solution. 130 parts of paraformaldehyde (4.33 mol) are then added to the reaction mixture. The reaction mixture is then kept at 20 ° C. with stirring for 24 hours. 1540 parts of a 50% strength aqueous, slightly yellowish, viscous solution of the reaction product of the formula are obtained
- Example 1 50 parts of a commercially available, crosslinked dextran (SEPHADEX E G 50) are mixed with 250 parts of the 50% strength aqueous solution of the reaction product according to regulation A, which has previously been brought to a pH of 3.5 with an aqueous 1N hydrochloric acid solution has been suspended. This slurry is kept under stirring at 20 ° C. for 30 minutes and then filtered off.
- SEPHADEX E G 50 crosslinked dextran
- the polysaccharide powder impregnated in this way is dried at 70 ° C. under reduced pressure.
- the condensation of the reaction product with the hydroxyl groups of the polysaccharide is then carried out at 100 ° C. for 75 minutes.
- the polysaccharide powder treated in this way is washed neutral with deionized water, dried at 70 ° C. under reduced pressure and finely ground (particle size 50-150 ⁇ m).
- a white powdery, crystalline, cationically modified polysaccharide 50 parts are obtained which have a degree of substitution of 0.60, an ion exchange capacity of 2.9 meq / g, a bulk volume of 2.3 ml / g, a swelling in water of 435 g / 1 and has very good flow properties and modified saccharide units of the formula contains, in which Sa stands for a saccharide residue.
- the bulk volume is determined as follows: A measuring cylinder of 10 ml content is filled with the respective material by tapping 10 times, then the weight is determined and converted to one liter.
- the swelling is determined as follows: 1 g of dry material is introduced into a 100 ml measuring cylinder and mixed with 100 ml deionized water and then left to stand for 14 hours, then the volume of the swollen material is read off the measuring cylinder.
- Stage I 50 parts of white dextrin are slurried with 250 parts of a 60% aqueous monomethylol acrylamide solution and 0.025 part of hydroquinone. This slurry, the pH of which is 2.5, is kept under stirring at 25 ° C. for 30 minutes. The slurry is then filtered off. The still moist, impregnated dextrin is stored at 20 ° C. for 24 hours and then dried at 70 ° C. under reduced pressure. The condensation reaction is then carried out at 120 ° C. for 60 minutes. After washing, drying and grinding as in Example 1 stated, 50 parts of a white, powdery, acrylic-modified polysaccharide, the modified saccharide units of the formula, are obtained contains, in which Sa stands for a saccharide residue. Stage II
- 50 parts of the acrylic-modified polysaccharide obtained according to the above step are slurried in 300 parts of deionized water.
- 80 parts of a 50% strength aqueous diethylamine solution are added to this slurry within 20 minutes, the temperature of the reaction mixture automatically increasing to 30 ° C. and a pH of 12.3 being established.
- the slurry is then heated to 50 ° C. and kept under stirring for 5 hours at this temperature, the pH of the slurry gradually falling to 11.8.
- the slurry is then filtered off.
- the polysaccharide treated in this way is washed with 500 parts of an aqueous 0.1N hydrochloric acid solution, then washed with deionized water until the pH of the filtrate is 6.0.
- modified polysaccharide is dried at 80 ° C under reduced pressure and ground (grain size 50-150 pm).
- 45 parts of a yellowish, powdery, cationically modified polysaccharide are obtained which have a degree of substitution of 0.25, an ion exchange capacity of 1.4 meq / g, a bulk volume of 665 g / l, a swelling in water of 2.8 ml / g and has very good flow properties and contains modified saccharide units of the formula (20).
- Example 3 The procedure is as described in Example 1, but a commercially available, crosslinked agarose (SEPHAROSE @ CL-6B) is used as the starting material. 45 parts of the cationically modified polysaccharide with cationic units of the formula (20) and very good flow properties are also obtained, but this has a degree of substitution of 0.21, an ion exchange capacity of 0.86 meq / g, a bulk volume of 625 g / l and one Has swelling in water of 7 ml / g.
- SEPHAROSE @ CL-6B commercially available, crosslinked agarose
- EXAMPLE 4 The procedure is as described in stages I and 11 of example 2, but the starting material used is white dextrin, which has been treated with an aqueous sodium carbonate solution before use, so that the pH of the white dextrin slurry is mixed with the monomethylolacrylamide solution and hydroquinone 7. 0 (instead of 2.5). 45 parts of the cationically modified polysaccharide with cationic units of the formula (20) and the properties given in stage II of Example 2 are also obtained, but which has an ion exchange capacity of 1.75 meq / g.
- EXAMPLE 5 The procedure is as described in stage 11 of Example 2, but 112 parts of a 50% aqueous sodium pyrosulfite solution which is made alkaline with sodium hydroxide are used (on the basis of 80 parts of the 50% aqueous diethylamine solution). The pH of the slurry is adjusted to 12.5 by adding an aqueous 2N sodium hydroxide solution. The slurry is heated to 50 ° C and kept at this temperature for 5 hours with stirring. The slurry is then filtered off. The polysaccharide treated in this way is washed and dried as indicated in step 11 of example 2.
- Example 6 The procedure described in Example 1 is followed, but 250 parts of the 50% strength aqueous solution of the reaction product according to regulation B (instead of A) are used and the still moist, impregnated polysaccharide powder (after filtration of the slurry) is stored for 24 Hours at 20 ° C., the condensation reaction and the working up of the treated polysaccharide powder (washing, drying and grinding) are also carried out as indicated in Example 1.
- 65 parts of a white, powdery, anionically modified polysaccharide are obtained which have a degree of substitution of 0.35, an ion exchange capacity of 2.0 meq / g, a bulk volume of 430 g / l, a swelling in water of 38 ml / g and very much has good flow properties and contains modified saccharide units of the formula (22).
- Example 7 20 parts of a commercially available, crosslinked agarose (SEPHAROSE® CL-6B) are dissolved in 100 parts of a 50% strength aqueous solution of the reaction product according to regulation B, which has previously been brought to a pH of 3 with an aqueous 1N hydrochloric acid solution , 5 has been discontinued. This slurry is kept under stirring at 20 ° C. for 30 minutes and then filtered off. The still moist, impregnated polysaccharide powder is stored at 20 ° C. for 24 hours. The subsequent drying and the condensation reaction as well as the processing of the treated polysaccharide powder (Washing, drying and grinding) is carried out as indicated in Example 1.
- SEPHAROSE® CL-6B crosslinked agarose
- EXAMPLE 8 The procedure is as described in Example 7, but 100 parts of a 50% strength aqueous solution of the reaction product according to preparation instructions C (instead of B) are used. After washing, drying and grinding, 19 parts of a yellowish, powdery, cationically modified polysaccharide are obtained which have a degree of substitution of 0.35, an ion exchange capacity of 1.4 meq / g, a bulk volume of 625 g / l, and swelling in water of 6 ml / g and has very good flow properties and modified saccharide units of the formula contains, in which Sa stands for a saccharide residue.
- Example 9 20 parts of a commercially available, crosslinked dextran (SEPHADEX® G-50) are mixed with 100 parts of a 50% strength aqueous solution of N-hydroxymethyl-dimethylphosphonopropionic acid amide, which has previously been brought to a pH of 3 with an aqueous 1N hydrochloric acid solution. 5 has been suspended. The procedure is then as described in Example 1, and after washing, drying and grinding, 18 parts of a white, powdery, modified polysaccharide are obtained which have a degree of substitution of 0.20. The phosphorus ester of the polysaccharide obtained is then slurried in 50 parts of an aqueous 2N sodium hydroxide solution, heated to the reflux temperature of approximately 100 ° C. and kept at this temperature for 1 hour with stirring.
- SEPHADEX® G-50 50% strength aqueous solution of N-hydroxymethyl-dimethylphosphonopropionic acid amide, which has previously been brought to a pH of 3 with an aqueous 1N hydrochlor
- the slurry is then cooled to 20 ° C and filtered off. After drying at 70 ° C. under reduced pressure, 17 parts of an anionically modified polysaccharide are obtained which have an ion exchange capacity of 0.43 meq / g, a bulk volume of 625 g / I, a swelling in water of 5 ml / g and very good Has flow properties and modified saccharide units of the formula contains, in which Sa stands for a saccharide residue.
- Example 10 The procedure described in Example 2 is followed, however, in stage I using a commercially available, uncrosslinked dextran (instead of white dextrin) and the reaction with the diethylamine solution in stage 11 is carried out at 50 ° C. for 20 minutes (instead of 5 Hours). After the slurry has been filtered off, the polysaccharide thus treated is dried under reduced pressure at 100 ° C., washed with 250 parts of alcohol, separated from the alcohol by decanting, and dried and ground as indicated in stage II of example 2.
- Example 11 6 parts of the modified polysaccharide according to Example 2 (stage II) are slurried in 50 parts of distilled water and kept at 20 ° C. for 30 minutes with stirring. The pH of the slurry is 6.0. The slurry is now filled into a chromatography column made of glass (diameter 1.27 cm, length 33 cm). The homogeneous bed of the modified polysaccharide as the stationary phase has a volume of 16.5 ml (filling height 13 cm).
- the modified polysaccharide is first rinsed with distilled water for one hour, then activated with an aqueous 0.1 N hydrochloric acid solution and then with a washed aqueous 0.5 N sodium chloride solution until neutral. Now the column is charged with 5 parts of a 0.5% aqueous solution of a commercially available, strongly sulfonated lignin sulfonate mixture from wood pulping, which has a pH of 10.0. At a flow rate of 100 ml ⁇ h -1 ⁇ cm-2, all components of the lignin sulfonate mixture are adsorbed on the modified polysaccharide.
- the components of the lignin sulfonate mixture with several eluents with increasing electrolyte concentrations as mobile phases from the modified polysaccharide as stationary phase separated by chromatography For this purpose, a fraction collector is used which separates the eluate into fractions of 4 ml each, the flow rate of the liquid phase through the stationary phase being 100 ml.h -1 . Cm -2 .
- the spectral adsorption of each of the 4 ml fractions is measured at 250 nm in order to enable a concentration comparison with respect to components of the lignin sulfonate mixture.
- the fractions that have no absorption are discarded. Fractions having absorption are collected.
- component II (1.8% of the mixture) has the characteristic -COO e band
- the component in addition to phenolic groups III 13.5% of the mixture
- the characteristic polar SO3 9 and S0 3 Na bands Due to their chromatographic behavior, corresponding to the higher pH values of the mobile phase, component IV (28.8%) of the mixture) is a polar lignin sulfonate fraction and component V (54.9% of the mixture) is a very polar, highly sulfonated lignin fraction represents.
- the modified polysaccharide in the chromatography column is rinsed with about 100 ml of an aqueous 0.1 N hydrochloric acid solution until the eluate has a pH of 1-2.
- the modified polysaccharide is available as a regenerated, stationary phase for further chromatographic separations.
- EXAMPLE 12 The procedure is as given in Example 11, but 7 parts (instead of 6 parts) of the modified polysaccharide according to Example 2 (stage 11) are slurried in 70 parts (instead of 50 parts) of dist. Water, receives a homogeneous bed of the stationary phase in the chromatography column, which has a volume of 20 ml (instead of 16.5 ml) and a filling height of 16.5 cm (instead of 12 cm), feeds the column with a commercially available, weak sulfonated (instead of strongly sulfonated) lignosulfonate mixture, elutes 4 components (instead of 5 components) of the ligninsulfonate mixture with the eluents specified in Table II below and uses a fraction collector which separates eluate fractions of 5 ml (instead of 4 ml).
- Table II The course of the chromatographic separation is given in Table II below:
- EXAMPLE 13 The procedure is as described in Example 11, but 6 parts of the modified polysaccharide according to Example 8 (instead of 6 parts of the modified polysaccharide according to Stage II of Example 2) are suspended in 70 parts (instead of 50 parts) of distilled water, and a homogeneous mixture is obtained Bed of the stationary phase in the chromatography column, which has a volume of 34 ml (instead of 16.5 ml) and a filling height of 26.5 cm (instead of 13 cm), elutes 6 components (instead of 5 components) of the lignosulfonate mixture with the in the the following table 111 eluents and uses a fraction collector that separates eluate fractions of 5 ml (instead of 4 ml).
- Table III The course of the chromatographic separation is given in Table III below:
- Example 14 7 parts of the modified polysaccharide according to Example 5 are slurried in 70 parts of distilled water and kept at 20 ° C. for 30 minutes with stirring. The pH of the slurry is 6.0. The slurry is now poured into a chromatography column made of glass (0 5 1.27 cm, L 33 cm). The homogeneous bed of the modified polysaccharide as a stationary phase has a volume of 24.5 ml (filling height 20 cm).
- the modified polysaccharide is first rinsed with distilled water for one hour, then activated with an aqueous 5% sodium carbonate solution and then neutralized with water washed. Now the column is charged with 5 parts of a 0.5% aqueous solution of a commercially available ligninamine mixture from wood pulping, which has a pH of 6.0. At a flow rate of 100 ml ⁇ h -1 ⁇ cm -2 all components of the lignin amine mixture are adsorbed on the modified polysaccharide.
- the components of the lignin amine mixture are chromatographically separated from the modified polysaccharide as the stationary phase with several elution agents (different buffer solutions with increasing pH values). For this purpose, fractions of 5 ml each of the corresponding eluates of the buffer solutions are collected by means of a fraction collector and the spectral absorption of the respective fraction is measured at 250 nm in order to enable a comparison of the concentrations with respect to components of the ligninamine mixture. In the course of the separation process, 4 components of the ligninamine are thus eluted.
- Table IV The course of the chromatographic separation of the ligninamine mixture with the eluents used is given in Table IV below.
- EXAMPLE 15 The procedure is as described in Example 14, but 1 part of the modified polysaccharide according to Example 6 (instead of 5) is used, and a homogeneous bed of the stationary phase is obtained which has a volume of 36 ml (instead of 24.5 ml) and one After rinsing, activating and washing the stationary phase, the column has a filling height of 28.5 cm (instead of 25 cm) and loads it with a dye mixture of 50% CI Basic Blue 3, 25% C.1. Basic Yellow 45 and 25% CI Basic Red 14. At a flow rate of 100 ml ⁇ h -1 ⁇ cm -2 the individual dyes of the mixture are completely retained on the modified polysaccharide.
- the individual dyes of the mixture are chromatographically separated from the modified polysaccharide as the stationary phase using a pH 4.0 buffer solution as the eluent.
- a pH 4.0 buffer solution as the eluent.
- 5 ml fractions of the corresponding eluates are collected and then the absorption of the respective fraction (at the respective absorption maxima of the different dyes) is measured in order to enable a concentration comparison with respect to components of the dye mixture. 4 components are thus eluted in the course of the separation process.
- the course of the chromatographic separation of the dye mixture is given in Table V below.
- Example 16 The procedure is as described in Example 14, but 5 parts of the modified polysaccharide according to Example 7 (instead of 5) are used and a homogeneous bed of the stationary phase is obtained which has a volume of 33.5 ml (instead of 24.5 ml) and has a filling height of 26.5 cm (instead of 20 cm).
- the column After rinsing, activating and washing the stationary phase as indicated in Example 1, the column is now charged with a dye mixture of 33% CI Basic Blue, 33% CI Basic Red 14 and 34% CI Basic Yellow 45.
- the chromatographic separation of the mixture is carried out as indicated in Example 15, but 3 (instead of 4) fractions of the dye mixture are separated and a buffer solution pH 4.5 (instead of 4.6) is used.
- the course of the chromatographic separation of the dye mixture is given in Table VI below.
- EXAMPLE 17 The procedure is as described in Example 14, but 7 parts of the modified polysaccharide according to Example 9 (instead of 5) are used and a homogeneous bed of the stationary phase is obtained which has a volume of 35 ml (instead of 24.5 ml) and one Filling height of 28.5 cm (instead of 20 cm).
- the column After rinsing, activating and washing the stationary phase as indicated in Example 14, the column is now charged with a dye mixture which contains 25% CI Basic Yellow 45 and 75% CI Basic Red 14.
- the chromatographic separation of the mixture is carried out as indicated in Example 15, but 5 (instead of 4) fractions of the dye mixture are separated and 3 buffer solutions pH 6, 4 and 2 (instead of a buffer solution pH 4.0) are used.
- the course of the chromatographic separation of the dye mixture is given in Table VII below.
- Example 18 A chromatography column with a diameter of 1.27 cm is filled with 7 parts of the cationically modified polysaccharide according to Example 8 (corresponding to 42 ml of modified polysaccharide and a filling height of 33 cm). Now at a flow rate of 50 ml ⁇ h -1 ⁇ cm -2 at 0.01 bar 250 ml of a 1.42% aqueous solution of crude cephalosporin C sodium salt is percolated through the column. The absorption value of the strongly brownish solution before percolation measured at 425 nm in a 1 cm cell is 1.65, while the percolate has an absorption value of only 0.935. The yield of percolated, purified cephalosporin C sodium salt, based on crude sodium salt, is 95.5%.
- Example 19 5 g of the cationically modified polysaccharide according to Example 8 are slurried in 60 ml of distilled water and kept under stirring at 20 ° C. for 30 minutes. The pH of the slurry is 6.0. The slurry is now poured into a chromatography column made of glass (diameter 1.3 cm, length 30 cm). The homogeneous bed of the cellulose material has a volume of 29 ml (filling height 23 cm). The column obtained has a flow rate of 720 ml ⁇ h -1 ⁇ cm -2 at a back pressure of 1.5 bar. The column is activated as indicated in Example 11 and then washed.
- the column is charged with an aqueous solution containing 1% humic acid.
- the humic acid used has a molecular weight of 600 to 1000 and an ash content of 10 to 15% (provenance FLUKA, catalog No. 53680, edition 1984).
- the humic acid solution is pumped through the column until the presence of humic acid at the outlet of the column is determined by means of a UV detector (measurement at 240 nm).
- the humic acid is separated off by elution with an aqueous ammonia solution which has a pH of 12.3. The elution process continues until the UV detector at the outlet of the column no longer shows humic acid.
- the load capacity of the cationically modified polysaccharide can be calculated on the basis of the humic acid content before and after the flow through the column. It is 50 mg humic acid per g separating material.
- the column is washed with distilled water until the pH of the wash water is 7 to 8 and then activated with an aqueous 0.1 N hydrochloric acid solution until the pH of the eluate is 1 to 2. Then the column is washed again with 50 ml of distilled water.
- the column is again charged with the aqueous 1% humic acid solution, as indicated above.
- the loadability after a regeneration step is 40 mg humic acid per g separating material.
- the load capacity after two regeneration steps is 37 mg humic acid per g separating material.
- EXAMPLE 20 The procedure is as given in Example 19, but the cationically modified polysaccharide according to Example 2 is used as the separating material.
- the load capacity is 36 mg and after a regeneration step 30 mg humic acid per g of separating material.
- Example 21 85 g of the humic acid used in Example 20 is dissolved in 500 ml of distilled water. 1 g of the cationically modified polysaccharide according to Example 1 is added to the humic acid solution with stirring. The mixture is kept at 20 ° C. for 20 minutes with stirring. After the batch has been left to stand, the humic acid still in solution can be determined by measuring the UV absorption at 250 nm and the amount of humic acid which is removed from the solution by the modified polysaccharide can be calculated.
- 42 mg humic acid per g modified polysaccharide can be removed from an aqueous solution.
- Example 22 The procedure of Example 21 is followed, but the batch (humic acid solution and cationically modified polysaccharide) is kept at 40 ° C. with stirring for 20 minutes. The amount of humic acid retained is 57 mg per g of modified polysaccharide.
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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CH328784 | 1984-07-06 | ||
CH3287/84 | 1984-07-06 |
Publications (3)
Publication Number | Publication Date |
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EP0167488A2 EP0167488A2 (de) | 1986-01-08 |
EP0167488A3 EP0167488A3 (en) | 1987-05-20 |
EP0167488B1 true EP0167488B1 (de) | 1990-07-25 |
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EP85810285A Expired - Lifetime EP0167488B1 (de) | 1984-07-06 | 1985-06-20 | Ionisch modifizierte Polysaccharide, Verfahren zu deren Herstellung und deren Verwendung |
Country Status (8)
Country | Link |
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US (1) | US5010184A (xx) |
EP (1) | EP0167488B1 (xx) |
JP (1) | JPH0699484B2 (xx) |
AU (1) | AU571979B2 (xx) |
CA (1) | CA1327568C (xx) |
DE (1) | DE3578834D1 (xx) |
IL (1) | IL75573A (xx) |
ZA (1) | ZA854648B (xx) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8110351B2 (en) | 2002-01-16 | 2012-02-07 | Invitrogen Dynal As | Method for isolating nucleic acids and protein from a single sample |
US8691969B2 (en) | 1994-12-12 | 2014-04-08 | Life Technologies As | Isolation of nucleic acid |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3619303A1 (de) * | 1986-06-07 | 1987-12-10 | Merck Patent Gmbh | Optisch aktive adsorbentien |
SE8902315D0 (sv) * | 1989-06-27 | 1989-06-27 | Pharmacia Ab | Anjonbytare |
SE9004129D0 (sv) * | 1990-12-21 | 1990-12-21 | Pharmacia Lkb Biotech | Anion exchanger |
DE102007025275A1 (de) | 2007-05-31 | 2008-12-04 | Qiagen Gmbh | Butendisäure oder deren Derivate zur Behandlung einer biologischen Probe |
DE102007025277A1 (de) | 2007-05-31 | 2008-12-04 | Qiagen Gmbh | Verfahren zur Stabilisierung einer biologischen Probe |
DE102007025276A1 (de) | 2007-05-31 | 2008-12-04 | Qiagen Gmbh | Aromatische Alkohole zur Behandlung einer biologischen Probe |
JP2013531987A (ja) | 2010-06-14 | 2013-08-15 | キアゲン ゲーエムベーハー | 固定生物学的試料から生体分子を抽出するためのターゲット細胞または組織を決定するための方法 |
Family Cites Families (14)
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US4264766A (en) * | 1877-09-19 | 1981-04-28 | Hoffmann-La Roche Inc. | Immunological diagnostic reagents |
NL77406C (xx) * | 1952-02-11 | |||
FR1365831A (fr) * | 1963-08-09 | 1964-07-03 | Warwick Chemical Yorkshire Ltd | Procédé de préparation d'un amidon modifié |
DE2650999A1 (de) * | 1975-11-14 | 1977-05-18 | Ciba Geigy Ag | N-methylolamide, ihre herstellung und verwendung |
DE2650966A1 (de) * | 1975-11-14 | 1977-05-26 | Ciba Geigy Ag | Gegebenenfalls veraetherte basische methylolverbindungen und deren salze |
US4178438A (en) * | 1975-11-14 | 1979-12-11 | Ciba-Geigy Aktiengesellschaft | Cationically modified, cellulose-containing materials |
SE420838B (sv) * | 1975-12-12 | 1981-11-02 | Pharmacia Fine Chemicals Ab | Dextranderivatgel i partikelform for separationsendamal |
US4060506A (en) * | 1976-04-27 | 1977-11-29 | A. E. Staley Manufacturing Company | Starch acrylamides and the method for preparing the same |
CH621999A5 (xx) * | 1976-06-24 | 1981-03-13 | Ciba Geigy Ag | |
FR2403098A1 (fr) * | 1977-09-19 | 1979-04-13 | Merieux Inst | Nouveau materiau capable de fixer de facon reversible des macromolecules biologiques, sa preparation et son application |
US4263146A (en) * | 1978-06-29 | 1981-04-21 | Ciba-Geigy Corporation | Process for removing cationic substances from aqueous solutions |
US4451613A (en) * | 1983-03-03 | 1984-05-29 | Minnesota Mining And Manufacturing Company | Ethylenically-unsaturated dextrin oligomers |
US4577013A (en) * | 1983-12-22 | 1986-03-18 | Ciba-Geigy Corporation | Ionically modified cellulose material, its preparation and its use |
US4664806A (en) * | 1985-01-22 | 1987-05-12 | Ciba-Geigy Corporation | Anionically modified polysaccharides chromatography agents |
-
1985
- 1985-06-18 AU AU43766/85A patent/AU571979B2/en not_active Ceased
- 1985-06-18 CA CA000484269A patent/CA1327568C/en not_active Expired - Fee Related
- 1985-06-19 IL IL75573A patent/IL75573A/xx not_active IP Right Cessation
- 1985-06-20 ZA ZA854648A patent/ZA854648B/xx unknown
- 1985-06-20 JP JP60135218A patent/JPH0699484B2/ja not_active Expired - Lifetime
- 1985-06-20 EP EP85810285A patent/EP0167488B1/de not_active Expired - Lifetime
- 1985-06-20 DE DE8585810285T patent/DE3578834D1/de not_active Expired - Lifetime
-
1989
- 1989-06-21 US US07/371,669 patent/US5010184A/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8691969B2 (en) | 1994-12-12 | 2014-04-08 | Life Technologies As | Isolation of nucleic acid |
US8110351B2 (en) | 2002-01-16 | 2012-02-07 | Invitrogen Dynal As | Method for isolating nucleic acids and protein from a single sample |
Also Published As
Publication number | Publication date |
---|---|
ZA854648B (en) | 1986-02-26 |
JPS6121101A (ja) | 1986-01-29 |
US5010184A (en) | 1991-04-23 |
CA1327568C (en) | 1994-03-08 |
DE3578834D1 (de) | 1990-08-30 |
EP0167488A3 (en) | 1987-05-20 |
IL75573A0 (en) | 1985-10-31 |
AU571979B2 (en) | 1988-04-28 |
AU4376685A (en) | 1986-01-09 |
IL75573A (en) | 1990-02-09 |
EP0167488A2 (de) | 1986-01-08 |
JPH0699484B2 (ja) | 1994-12-07 |
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